Obtenção e caracterização de nanopartículas de argilominerais

Natural nanoclays are of great interest particularly for the production of polymer-based nanocomposites. In this work, kaolinite clays from two natural deposits in the State of the Rio Grande do Norte and Paraiba were purified with thermal treatment and chemical treatments, and characterized. Front to the gotten data, had been proposals methodologies for elimination or reduction of coarse particle texts, oxide of iron and organic substance. These methodologies had consisted of the combination of operations with thermal treatments, carried through in electric oven, and acid chemical attacks with and hydrogen peroxide. The Analyzers Thermogravimetric was used to examine the thermal stability of the nanoclays. The analysis indicated weight losses at temperatures under 110 ºC and over the temperature range of 350 to 550 ºC. Based on the thermal analysis data, the samples were submitted to a thermal treatment at 500 °C, for 8 h, to remove organic components. The X-ray diffraction patterns indicated that thermal treatment under 500 °C affect the basic structure of kaolinite. The BET surface area measurements ranged from 32 to 38 m2/g for clay samples with thermal treatment and from 36 to 53 m2/g for chemically treated samples. Thus, although the thermal treatment increased the surface area, through the removal of organic components, the effect was not significant and chemical treatment is more efficient, not affect the basic structure of kaolinite, to improve particle dispersion. SEM analysis confirms that the clay is agglomerated forming micron-size particles

Desevolvimento de nanocompósitos de poli(metacrilato de metila)/argila processados por mistura no estado fundido

Poly(methyl methacrylate)/clay nanocomposites were prepared by melt mixing using a montmorillonite-rich clay (MMT). The clay in natura was treated with acrylic acid to facilitate the dispersion in the polymer matrix. A masterbatch of PMMA/clay was prepared and combined with the pure PMMA and then subjected to extrusion process using singlescrew and twin-screw extruders followed by injection. Nanocomposites were processed with clay contents of 1, 3, 5 and 8 wt.%. The effect of shear processing on the morphology of the nanocomposites was evaluated by XRD, SEM and TEM. Thermal and mechanical properties of the nanocomposites were investigated through TGA, DSC, HDT, VICAT, tensile and impact tests, to evaluate the effect of the addition of clay to the PMMA matrix. Flammability tests were also conducted to investigate the effect of the addition of clay on the flame retardation properties. SEM images of the nanocomposites indicated the presence of clay agglomerates, which resulted in the reduction of properties such as thermal stability, mechanical strength and impact resistance, and increased the rate of burning for materials processed by both extrusion routes

Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium